Crude oil is the world's main source of hydrocarbons used as fuel and petrochemical feedstock. At the same time, petroleum and petroleum based products are also a major source for air and water pollution today. To address growing concerns surrounding pollution caused by petroleum and petroleum based products, many countries have implemented strict regulations on petroleum products, particularly on petroleum refining operations and the allowable concentrations of specific pollutants in fuels, such as the allowable sulfur and nitrogen content in gasoline fuels. While the exact compositions of natural petroleum or crude oils vary significantly, all crude oils contain some measurable amount of sulfur compounds and most crude oils also contain some measurable amount of nitrogen compounds. In addition, crude oils may also contain oxygen, however oxygen content of most crude is generally low. Sulfur concentrations in crude oils are typically less than about 5 percent by weight, with most crude oils having sulfur concentrations in the range from about 0.5 to about 1.5% by weight. Nitrogen concentrations of most crude oils are usually less than 0.2 percent by weight, but can be as high as 1.6% by weight. In the United States, motor gasoline fuel is regulated to have a maximum total sulfur content of less than 10 ppm sulfur, thus removal of sulfur is a key concern.
Crude oils are refined in oil refineries to produce transportation fuels and petrochemical feedstocks. Typically fuels for transportation are produced by processing and blending of distilled fractions from the crude oil to meet the particular end use specifications. Because most of the crudes generally available today have high concentrations of sulfur, the distilled fractions will require some desulfurization to yield products which meet various performance specifications and/or environmental standards.
The sulfur-containing organic compounds present in crude oils and resulting refined fuels can be a major source of environmental pollution. The sulfur compounds are typically converted to sulfur oxides during the combustion process, which in turn can produce sulfur oxyacids and contribute to particulate emissions, both of which are desired to be reduced.
One method for reducing particulate emissions can include the addition of various oxygenated fuel blending compounds and/or compounds that contain few or no carbon-to-carbon chemical bonds, such as methanol and dimethyl ether. Most of these fuel blending compounds, however, suffer in that they can have high vapor pressures, can be nearly insoluble in diesel fuel, and/or have poor ignition quality, as indicated by their cetane numbers.
Hydrotreating and hydrogenation are alternate techniques currently used for the removal of sulfur and/or nitrogen from hydrocarbons. Diesel fuels that have been treated by chemical hydrotreating and/or hydrogenation to reduce the content of sulfur and aromatic compounds frequently have a reduced fuel lubricity, which in turn can cause excessive wear of fuel pumps, injectors and other moving parts that come in contact with the fuel under high pressures.
For example, middle distillates (a distillate fraction that nominally boils in the range of about 180-370° C.) can be used directly as a fuel, or alternatively can be used as a blending component of fuel for use in compression ignition internal combustion engines (i.e., diesel engines). The middle distillate fraction, however, typically include between about 1 and 3% by weight sulfur, which is greater than allowable sulfur concentration of middle distillate fractions, which, since 1993, have been reduced in Europe and United States to between a currently allowed amount of about 5-50 part per million weight (ppmw) levels from the 3000 ppmw level.
Conventional techniques currently employed for the removal of sulfur and nitrogen compounds typically still require the subsequent recovery and/or disposal of the sulfur and nitrogen containing compounds that are removed from the hydrocarbons. In order to comply with the increasingly stringent regulations for ultra-low sulfur content fuels, refiners must make fuels having even lower sulfur levels at the refinery gate so that they can meet the strict specifications after blending.
Low pressure conventional hydrodesulfurization (HDS) processes can be used to remove a major portion of the sulfur from petroleum distillates for the eventual blending of refinery transportation fuels. These desulfurization units, however, are not very efficient at removing sulfur from compounds at mild conditions (i.e., up to about 30 bar pressure), or when the sulfur atom is sterically hindered, as is the case in multi-ring aromatic sulfur compounds. This is particularly true where the sulfur heteroatom is hindered by two alkyl groups (e.g., 4,6-dimethyldibenzothiophene). Because of the difficulty in the removal of sulfur from sterically hindered compounds, dibenzothiophenes predominate at low sulfur levels such as 50 to 100 ppmw. Severe operating conditions (e.g., high hydrogen partial pressure, high temperature, and/or high catalyst volume) typically must be utilized in order to remove the sulfur from these refractory sulfur compounds. Increasing the hydrogen partial pressure can only be achieved by increasing the recycle gas purity, or new grassroots units must be designed, which can be a very a costly option. The use of severe operating conditions typically results in decreased yield, reduced catalyst life cycle, and product quality deterioration (e.g., color), and therefore are typically sought to be avoided.
Conventional methods for petroleum upgrading, specifically for the removal of sulfur and/or nitrogen containing compounds, however, typically suffer from various limitations and drawbacks. For example, hydrogenative methods typically require large amounts of hydrogen gas to be supplied from an external source to attain desired level of upgrading and conversion. These methods can also suffer from premature or rapid deactivation of catalyst, as is typically the case during the hydrotreatment of a heavy feedstock and/or hydrotreatment under harsh conditions, thus requiring regeneration of the catalyst and/or addition of new catalyst, which in turn can lead to process unit downtime. Thermal methods, on the other hand, frequently suffer from the production of large amounts of coke as a byproduct and a limited ability to remove impurities, such as, sulfur and nitrogen, in addition to the large energy requirements associated with these processes. Additionally, thermal methods require specialized equipment suitable for severe conditions (high temperature and high pressure), and require the input of significant energy, thereby resulting in increased complexity and cost.
Thus, there exists a need to provide methods for the upgrading of hydrocarbon feedstocks, particularly processes for the desulfurization and/or denitrogenation of hydrocarbon feedstocks that use low severity conditions that can also provide means for the recovery and disposal of usable sulfur and/or nitrogen compounds.